Supported Hydrotreating Catalysts Having Enhanced Activity

ABSTRACT

This invention provides supported catalysts comprising a carrier, phosphorus, at least one Group VI metal, at least one Group VIII metal, and a polymer. In the catalyst, the molar ratio of phosphorus to Group VI metal is about 1:1.5 to less than about 1:12, the molar ratio of the Group VI metal to the Group VIII metal is about 1:1 to about 5:1, and the polymer has a carbon backbone and comprises functional groups having at least one heteroatom. Also provided are a process for preparing such supported catalysts, as well as methods for hydrotreating, hydrodenitrogenation, and/or hydrodesulfurization, using supported catalysts.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.17/520,205, filed on Nov. 5, 2021, now allowed; which in turn is acontinuation-in-part of U.S. patent application Ser. No. 14/430,146,filed on Mar. 20, 2015, now abandoned; which in turn is the NationalStage of International Patent Appl. No. PCT/EP2013/070826, filed on Oct.7, 2013; which in turn claims the benefit of U.S. Provisional PatentAppl. No. 61/712,108, filed on Oct. 10, 2012; the disclosures of whichare incorporated herein by reference.

TECHNICAL FIELD

This invention relates to supported catalysts formed from concentratedsolutions comprising a Group VI metal, a Group VIII metal, andphosphorus.

BACKGROUND

A variety of catalysts for hydrotreating, hydrodesulfurization, and/orhydrodenitrogenation are known and/or are commercially available. Manyof these catalysts, some of which contain molybdenum, nickel or cobalt,and phosphorus, are supported on carriers, and are usually prepared bypore volume impregnation. The art continually strives to make differentand better catalysts, especially with higher activities forhydrotreating, hydrodesulfurization, and/or hydrodenitrogenation.

Hydroprocessing catalysts are typically prepared by impregnation of aporous carrier material with a solution containing active metals,followed by either drying or calcination. Calcined catalysts tend toexhibit a strong metal-support interaction, which results in a highmetal dispersion. However, it is theorized that strong metal-supportinteraction in calcined catalysts results in a lower intrinsic activityof the catalyst. Non-calcined catalysts typically show a lowmetal-support interaction and an intrinsically high activity. Due to thelow metal-support interaction in non-calcined catalysts, the metals tendto aggregate (poor metal dispersion).

SUMMARY OF THE INVENTION

This invention provides processes for preparing supported catalysts fromconcentrated solutions comprising Group VI metal, Group VIII metal, andphosphorus, and catalysts prepared by such processes. Catalysts preparedaccording to the invention exhibit high activity in hydrodesulfurizationand hydrodenitrification. It has been suggested that in the catalysts ofthe invention, which are polymer-modified, the hydrogenation metals aremore dispersed than in similar catalysts in absence of polymermodification.

An embodiment of this invention is a supported catalyst. The supportedcatalyst comprises a carrier, phosphorus, at least one Group VI metal,at least one Group VIII metal, and a polymer. In the catalyst, the molarratio of phosphorus to Group VI metal is about 1:1.5 to less than about1:12, the molar ratio of the Group VI metal to the Group VIII metal isabout 1:1 to about 5:1. The polymer in the catalyst has a carbonbackbone and comprises functional groups having at least one heteroatom.

Other embodiments of this invention include processes for forming thejust-described supported catalysts, as well as methods forhydrotreating, hydrodenitrogenation, and/or hydrodesulfurization, usingthe just-described supported catalysts.

These and other embodiments and features of this invention will be stillfurther apparent from the ensuing description, drawings, and appendedclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a Raman spectrum providing evidence of polymerization in acatalyst prepared in Example 5.

FIG. 2 shows Raman spectra providing evidence of polymerization in someof the samples prepared in Examples 8 and 9.

FIGS. 3-1 to 3-5 show cross sections from SEM-EDX measurements ofcatalyst particles prepared as in Examples 14 and 15.

FURTHER DETAILED DESCRIPTION OF THE INVENTION

Throughout this document, the phrases “hydrogenation metal” and“hydrogenation metals” refer to the Group VI metal or metals and theGroup VIII metal or metals collectively. As used throughout thisdocument, the term “Group VI metal” refers to the metals of Group VIIIAs used throughout this document, the phrases “as the Group VI metaltrioxide,” “reported as the Group VI metal trioxide,” “calculated as theGroup VI metal trioxide,” “expressed as their oxides,” and analogousphrases for the Group VIII metals as their monoxides and phosphorus asphosphorus pentoxide (P₂O₅) refer to the amount or concentration ofGroup VI metal, Group VIII metal, or phosphorus, where the numericalvalue is for the respective oxide, unless otherwise noted. For example,nickel carbonate may be used, but the amount of nickel is stated as thevalue for nickel oxide.

The impregnation solutions used in the practice of this inventioncomprise a polar solvent, phosphorus, at least one Group VI metal, andat least one Group VIII metal, where the molar ratio of phosphorus toGroup VI metal is about 1:1.5 to less than about 1:12, and where themolar ratio of the Group VI metal to the Group VIII metal is about 1:1to about 5:1.

The Group VI metal is molybdenum, tungsten, and/or chromium; preferablymolybdenum or tungsten, more preferably molybdenum. The Group VIII metalis iron, nickel and/or cobalt, preferably nickel and/or cobalt.Preferred mixtures of metals include a combination of nickel and/orcobalt and molybdenum and/or tungsten. When hydrodesulfurizationactivity of the catalyst is to be emphasized, a combination of cobaltand molybdenum is advantageous and preferred. When hydrodenitrogenationactivity of the catalyst is to be emphasized, a combination of nickeland molybdenum and/or tungsten is advantageous and preferred. Anotherpreferred combination of hydrogenation metals is nickel, cobalt andmolybdenum.

The Group VI metal compound can be an oxide, an oxo-acid, or an ammoniumsalt of an oxo or polyoxo anion; these Group VI metal compounds areformally in the +6 oxidation state when the metal is molybdenum ortungsten. Oxides and oxo-acids are preferred Group VI metal compounds.Suitable Group VI metal compounds in the practice of this inventioninclude chromium(III) oxide, ammonium chromate, ammonium dichromate,molybdenum trioxide, molybdic acid, ammonium molybdate, ammoniumpara-molybdate, tungsten trioxide, tungstic acid, ammonium metatungstatehydrate, ammonium para-tungstate, and the like. Preferred Group VI metalcompounds include chromium(III) oxide, molybdenum trioxide, molybdicacid, ammonium para-tungstate, tungsten trioxide and tungstic acid.Mixtures of any two or more Group VI metal compounds can be used.

The Group VIII metal compound is usually an oxide, carbonate, hydroxide,or a salt. Suitable Group VIII metal compounds include, but are notlimited to, iron oxide, iron hydroxide, iron nitrate, iron carbonate,iron hydroxy-carbonate, iron acetate, iron citrate, cobalt oxide, cobalthydroxide, cobalt nitrate, cobalt carbonate, cobalt hydroxy-carbonate,cobalt acetate, cobalt citrate, nickel oxide, nickel hydroxide, nickelnitrate, nickel carbonate, nickel hydroxy-carbonate, nickel acetate, andnickel citrate. Preferred Group VIII metal compounds include ironhydroxide, iron carbonate, iron hydroxy-carbonate, cobalt hydroxide,cobalt carbonate, cobalt hydroxy-carbonate, nickel hydroxide, nickelcarbonate, and nickel hydroxy-carbonate. Mixtures of two or more GroupVIII metal compounds can be used.

In the practice of this invention, the phosphorus compound is soluble ina polar solvent, and is typically an acidic phosphorus compound,preferably a water soluble acidic phosphorus compound, particularly anoxygenated inorganic phosphorus-containing acid. Examples of suitablephosphorus compounds include metaphosphoric acid, pyrophosphoric acid,phosphorous acid, orthophosphoric acid, triphosphoric acid,tetraphosphoric acid, and precursors of acids of phosphorus, such asammonium hydrogen phosphates. Mixtures of two or more phosphoruscompounds can be used. The phosphorus compound may be used in liquid orsolid form. In some embodiments, the phosphorus compound is preferably awater-soluble compound. A preferred phosphorus compound isorthophosphoric acid (H₃PO₄).

In this invention, the polar solvent can be protic or aprotic, and isgenerally a polar organic solvent and/or water. Mixtures of polarsolvents can be used, including mixtures comprising an aprotic solventand a protic solvent. Suitable polar solvents include water, methanol,ethanol, n-propanol, isopropyl alcohol, acetonitrile, acetone,tetrahydrofuran, ethylene glycol, dimethylformamide, dimethylsulfoxide,methylene chloride, and the like, and mixtures thereof. Preferably, thepolar solvent is a protic solvent; more preferably, the polar solvent iswater or an alcohol, such as ethanol or isopropyl alcohol. Water is apreferred polar solvent.

When a monomer and a carrier are brought together and the monomer ispolymerized before being contacted with an impregnation solution, onlythe monomer needs to be soluble in the polar solvent used prior topolymerization. It is preferred to employ the same polar solvent todissolve the monomer and to form the impregnation solution, althoughdifferent solvents can be used if desired. When an impregnation solutionand a carrier are brought together to form an impregnated carrier priorto contact with the monomer, the monomer needs to be soluble in a polarsolvent that may be the same or different than the polar solvent of theimpregnation solution; use of the same polar solvent to dissolve themonomer and to form the impregnation solution is preferred, althoughdifferent solvents can be used if desired.

Polar solvents that form impregnation solutions must be able to dissolvethe phosphorus compounds, Group VI metal compounds, and Group VIII metalcompounds that are used in forming the impregnation solutions used inthe practice of this invention.

When a monomer species and at least one phosphorus compound, at leastone Group VI metal compound, at least one Group VIII metal compound arebrought together prior to polymerization, the monomer species should besoluble in the solution containing a polar solvent, phosphorus, at leastone Group VI metal compound, and at least one Group VIII metal compound.Generally, this solubility property for the monomer species is similarto the solubility of the monomer species in the polar solvent without atleast one phosphorus compound, at least one Group VI metal compound, andat least one Group VIII metal compound in solution. When an impregnationsolution is brought into contact with the carrier and monomer speciesduring polymerization, the same solubility considerations apply; namely,that the monomer species present should be soluble in the polar solventin the presence of the at least one phosphorus compound, at least oneGroup VI metal compound, and at least one Group VIII metal compound.

Throughout this document, the term “monomer” is synonymous with thephrase “monomer species.” The monomer species has carbon-carbonunsaturation as the polymerizable moiety, and at least one functionalgroup comprising at least one heteroatom. It is theorized that theheteroatom(s) may form a bond or interaction with a metal ion, thoughformation of bonds or interactions is not required. Preferred monomersinclude functional groups which have one or more lone pairs ofelectrons. Preferably, the functional group of the monomer speciescomprises nitrogen, oxygen, phosphorus, and/or sulfur. Examples ofsuitable functional groups include hydroxyl groups, carboxyl groups,carbonyl groups, amine groups, amide groups, nitrile groups, amino acidgroups, phosphate groups, thiol groups, sulfonic acid groups, and thelike. Preferred functional groups include hydroxyl groups andcarboxyl-containing groups, especially carboxylic acid groups, estergroups, amido groups, and hydroxyl groups; more preferred are carboxylicacid groups.

Thus, suitable monomer species include acrylic acid, maleic acid,fumaric acid, crotonic acid, pentenoic acid, methacrylic acid,2,3-dimethacrylic acid, 3,3-dimethacrylic acid, allyl alcohol,2-sulfoethyl methacrylate, n-propyl acrylate, hydroxymethyl acrylate,2-hydroxyethyl acrylate, 2-carboxyethyl acrylate, 3-ethoxy-3-oxopropylacrylate, methylcarbamylethyl acrylate, 2-hydroxyethyl methacrylate,N-vinylpyrrolidone, acrylamide, methacrylamide, N-isopropylacrylamide,N-vinylacetamide, N-vinyl-N-methylacetamide, N-hydroxymethyl acrylamide,N-hydroxyethyl acrylamide, N-methoxymethyl acrylamide, N-ethoxymethylacrylamide, vinyl sulfate, vinyl sulfonic acid, 2-propene-1-sulfonicacid, vinyl phosphate, vinyl phosphonic acid, dimethyl allyl phosphate,diethyl allyl phosphate, and the like. Preferred monomer species includeacrylic acid, maleic acid, 2-carboxyethyl acrylate, and N-hydroxyethylacrylamide, particularly acrylic acid. Mixtures of two or more monomerspecies can be employed.

The amount of monomer used to form the catalysts of this invention isexpressed as wt % relative to the total weight of the other componentsused to form the catalyst, excluding the polar solvent. As usedthroughout this document, the phrases “other components used to form thecatalyst” and “other catalyst components” refer to the carrier and thechemical substances that provide the hydrogenation metals and phosphorusto the catalyst. For example, if the total weight of the othercomponents of the catalyst (other than the polar solvent) is 100 grams,10 wt % of monomer is 10 grams. In the practice of this invention, theamount of monomer is generally about 1.5 wt % or more, preferably in therange of about 1.5 wt % to about 35 wt %, relative to the total weightof the other components of the catalyst excluding the polar solvent,although amounts outside these ranges are within the scope of theinvention. More preferably, the amount of monomer is in the range ofabout 3 wt % to about 27 wt %, and even more preferably in the range ofabout 5 wt % to about 20 wt % relative to the total weight of the othercomponents of the catalyst excluding the polar solvent.

An inhibitor (e.g., a radical scavenger) can be included with themonomer to prevent premature polymerization of the monomer species.Suitable inhibitors will vary with the particular monomer(s).Appropriate inhibitors will not have an adverse effect on the at leastone phosphorus compound, at least one Group VI metal compound, and atleast one Group VIII metal compound, when present in the mixture beforepolymerization is initiated. Desirably, the inhibitor is neutralized orremoved (e.g., by evaporation or introduction of an initiator) when itis desired to start the polymerization reaction.

Although the components used in forming an impregnation solution can becombined in any order, it is recommended and preferred that onecomponent is suspended or dissolved in the polar solvent prior to theintroduction of the other components. Preferably, the Group VIII metalcompound is introduced first; more preferably, the Group VI metalcompound is introduced after the Group VIII metal compound. Thephosphorus compound may be introduced at any point, but preferably isintroduced after the Group VI compound and the Group VIII compound havebeen introduced. Stirring may be employed when forming the solution, butcan be stopped once the solution is homogeneous. Similar considerationsapply when a monomer and at least one phosphorus compound, at least oneGroup VI metal compound, and at least one Group VIII metal compound arebrought together; it is preferable to combine the compounds of thehydrogenation metals with the polar solvent, then add the phosphoruscompound, followed by the monomer.

Combining of the components of an impregnation solution can be done atambient conditions, i.e., room temperature and ambient pressure.Elevated temperatures are sometimes necessary to assist in thedissolution of the components, particularly the Group VI compound andthe Group VIII compound. Such elevated temperatures are typically in therange of about 50° C. to about 95° C., preferably about 60° C. to about95° C. Temperatures in excess of about 95° C. and/or elevated pressurescan be applied (e.g., hydrothermal preparation), but are not required.If a monomer for which polymerization is thermally initiated is to beincluded in the solution, either the temperature to which the solutionis heated is kept below the temperature at which polymerization isinitiated, or, preferably, the monomer species is added after anyheating of the solution is completed.

It is convenient to prepare solutions having concentrations that arepractical for further intended use of the solution. These solutions canbe employed, as embodied in this invention, to form a supportedcatalyst. Suitable concentrations based on the Group VI metal (or totalthereof, if more than one Group VI metal is present in the composition),are typically in the range of about 1.39 mol/L to about 6 mol/L,preferably in the range of about 2.1 mol/L to about 4.2 mol/L.

Methods for preparing more-concentrated impregnation solutions areknown, and are described for example in International Publication No. WO2011/023668.

The impregnation solutions for the invention, formed as described above,are solutions comprising a Group VI metal, a Group VIII metal, andphosphorus, in a polar solvent. The concentrations of the Group VImetal, Group VIII metal, phosphorus and, and the preferences thereforare as described above. In these solutions, the molar ratio ofphosphorus to Group VI metal is about 1:1.5 to less than about 1:12,preferably about 1:2.5 to less than about 1:12, and the molar ratio ofthe Group VI metal to the Group VIII metal is about 1:1 to about 5:1.

Without wishing to be bound by theory, a mixture of species is believedto be present in the impregnation solutions for this invention. At thistime, not all of the species are well characterized. In this connection,for examples of species present in solutions containing molybdenum andphosphorus, see J. Bergwerff, Ph.D. thesis, Utrecht University, TheNetherlands, 2007, Chapter 2C.

When mixtures of reagents are used in forming the solutions, asmentioned above, a mixture of species having different metals will bepresent in the solution. For example, if a molybdenum compound and atungsten compound are used, the product solution will include molybdenumand tungsten. In another example, if a cobalt compound and a nickelcompound are used, the solution will include cobalt and nickel. Mixturesof reagents such that Group VI metal compounds in which the Group VImetals of the compounds are different and Group VIII metal compounds inwhich the Group VIII metals of the compounds are different can be usedin forming the solution compositions if desired.

The processes of the invention for forming catalysts comprise I)bringing together a carrier, one or more monomer species, a polarsolvent, at least one phosphorus compound, at least one Group VI metalcompound, and at least one Group VIII metal compound, and optionally aninitiator, in any of the following combinations:

-   -   a carrier, one or more monomer species, a polar solvent, and        optionally an initiator,    -   a carrier, one or more monomer species, at least one phosphorus        compound, at least one Group VI metal compound, and at least one        Group VIII metal compound, and optionally an initiator, or    -   a carrier and an impregnation solution, forming an impregnated        carrier, followed by mixing the impregnated carrier with one or        more monomer species and optionally an initiator,        to form a monomer-containing mixture, where said monomer species        is soluble in the polar solvent and has carbon-carbon        unsaturation and at least one functional group comprising at        least one heteroatom. Step II) comprises polymerizing the        monomer species in the monomer-containing mixture to form a        polymerized product. Step III) is performed when I) does not        include at least one phosphorus compound, at least one Group VI        metal compound, and at least one Group VIII metal compound, and        comprises either    -   contacting an impregnation solution and the monomer-containing        mixture during the polymerizing in II), or    -   contacting the polymerized product and an impregnation solution.        A supported catalyst is formed. In the processes, the molar        ratio of phosphorus to Group VI metal is about 1:1.5 to less        than about 1:12, where the molar ratio of the Group VI metal to        the Group VIII metal is about 1:1 to about 5:1. Impregnation        solutions employed in the process comprise a polar solvent,        phosphorus, at least one Group VI metal, and at least one Group        VIII metal. Removal of excess solvent from the supported        catalyst, e.g., by drying, is a recommended further step.

A feature of this invention is that there is no aggregation of carrierparticles in the processes of the invention for forming catalysts. Inother words, the carrier particles are unaltered in size and shape bythe processes of the invention for forming catalysts. For example,carrier particles with an average particle size of about 2 mm becomecatalyst particles with an average particle size of about 2 mm.

In the processes of the invention for forming catalysts, all of thecomponents in the impregnation solution must be dissolved beforeinitiating the impregnation step. When at least one phosphorus compound,at least one Group VI metal compound, and at least one Group VIII metalcompound form part of the monomer-containing mixture, the monomerspecies is preferably combined with the mixture after any heating of themixture is finished. For monomers of thermally-initiatedpolymerizations, the temperature during formation of themonomer-containing mixtures are kept below the initiation temperaturefor polymerization.

The monomer-containing mixture includes at least one carrier and atleast one monomer species. At least one phosphorus compound, at leastone Group VI metal compound, and at least one Group VIII metal compound,or an impregnation solution are optionally included with the carrier andone or more monomer species in forming the monomer-containing mixture.Inclusion of the at least one phosphorus compound, at least one Group VImetal compound, and at least one Group VIII metal compound (sometimes asan impregnation solution) in the monomer-containing mixture isrecommended and preferred. When at least one phosphorus compound, atleast one Group VI metal compound, and at least one Group VIII metalcompound (sometimes as an impregnation solution) are not included in themonomer-containing mixture, an impregnation solution can be mixed withthe polymerized product of the monomer-containing solution;alternatively, an impregnation solution can be brought into contact withthe monomer-containing mixture during polymerization.

In the processes of this invention, the polymerization of the monomerspecies to form the polymer typically employs at least one initiator.Initiators include heat, radiation (e.g., UV), chemical substances, andcombinations of these. When the initiator is a chemical substance, itusually remains with the supported catalyst, and may affect catalystperformance. Thus, when more than one initiator can be chosen, it may beuseful to run tests to determine which combination of initiator(s) andselected monomer(s) allows for optimal catalyst performance. Anotherconsideration is that the selected initiator(s) and monomer(s) shouldnot adversely affect the solubility of the phosphorus, Group VI metal,and/or Group VIII metal compounds in the impregnation solution (e.g., bycausing precipitation). For example, in the polymerization of acrylicacid with persulfate salts as initiators, it was found that potassiumpersulfate was a better initiator than ammonium persulfate for acatalyst containing nickel, molybdenum, and phosphorus. The effect of aparticular initiator may vary with the concentration of hydrogenationmetals present in the catalyst, the monomer, and the conditions underwhich catalysis is performed.

Suitable initiators also depend on the (polymerization) reactivity ofthe selected monomer(s). For example, ammonium persulfate or potassiumpersulfate in combination with an increase in temperature from roomtemperature to 80° C. is a suitable combination of initiators forpolymerization of acrylic acid. However, for monomers that polymerizeless readily, a different type of initiator or a different combinationof initiators may be required.

As used throughout this document, the term “carrier” is used to mean acatalyst support, and the term “carrier” can be used interchangeablywith the term “support”. Throughout this document, the term “carrier”refers to a carrier which is in the solid form or is pre-shaped. Such acarrier remains predominantly in the solid form when contacted with apolar solvent. The term does not refer to precursor salts, such assodium aluminate, which dissolve almost completely in a polar solvent.The carrier is generally an inorganic oxide which is a particulateporous solid, and the carrier may be composed of conventional oxides,e.g., alumina, silica, silica-alumina, alumina with silica-aluminadispersed therein, alumina-coated silica, silica-coated alumina,magnesia, zirconia, boria, and titania, as well as mixtures of theseoxides. Suitable carriers also include transition aluminas, for examplean eta, theta, or gamma alumina. Preferred carriers include silica,alumina, silica-alumina, alumina with silica-alumina dispersed therein,alumina-coated silica, or silica-coated alumina, especially alumina oralumina containing up to about 20 wt % of silica, preferably up to about12 wt % of silica. A carrier containing a transition alumina, forexample an eta, theta, or gamma alumina, is particularly preferred, anda gamma-alumina carrier is most preferred.

The carrier is normally employed in a conventional manner in the form ofspheres or, preferably, extrudates. Examples of suitable types ofextrudates have been disclosed in the literature; see for example U.S.Pat. No. 4,028,227. Highly suitable for use are cylindrical particles(which may or may not be hollow) as well as symmetrical and asymmetricalpolylobed particles (2, 3 or 4 lobes). Carrier particles are typicallycalcined at a temperature in the range of about 400° to about 850° C.before use in forming the catalysts of this invention.

Although particular pore dimensions are not required in the practice ofthis invention, the carrier's pore volume (measured via N₂ adsorption)will generally be in the range of about 0.25 to about 1 mL/g. Thespecific surface area will generally be in the range of about 50 toabout 400 m²/g, preferably about 100 to about 300 m²/g (measured usingthe BET method). Generally, the catalyst will have a median porediameter in the range of about 7 nm to about 20 nm, preferably in therange of about 9 nm to about 20 nm, as determined by N₂ adsorption.Preferably, about 60% or more of the total pore volume will be in therange of approximately 2 nm from the median pore diameter. The figuresfor the pore size distribution and the surface area given above aredetermined after calcination of the carrier at about 500° C. for onehour.

The carrier particles typically have an average particle size of about0.5 mm to about 5 mm, more preferably about 1 mm to about 3 mm, andstill more preferably about 1 mm to about 2 mm. Because the size andshape of the carrier is not altered by the process for forming thecatalyst, the catalyst generally has an average particle size of about0.5 mm to about 5 mm, more preferably about 1 mm to about 3 mm, andstill more preferably about 1 mm to about 2 mm.

The amount of carrier used to form the catalysts of this invention isabout 40 wt % to about 80 wt %, preferably about 50 wt % to about 70 wt%, and more preferably about 60 wt % to about 70 wt %, relative to thetotal weight of the carrier, hydrogenation metals, and phosphorus, wherethe hydrogenation metals and phosphorus are expressed as their oxides,i.e., excluding the polar solvent and the monomer species.

Methods for impregnating the carrier are known to the skilled artisan.Preferred methods include co-impregnation of at least one phosphoruscompound, at least one Group VI metal compound, and at least one GroupVIII metal compound. In the processes of this invention for formingcatalysts, only one impregnation step is needed. In a singleimpregnation step, once the carrier and impregnation solution arebrought together, the mixture is usually homogenized until virtually allof the impregnation solution is taken up into the catalyst. In thistechnique, which is known in the art as pore volume impregnation or asincipient wetness impregnation, the impregnation solution will be takenup virtually completely by the pores of the catalyst, which makes for anefficient use of chemicals, and avoids dust in the product.

There can be a wide number of variations on the impregnation method.Thus, it is possible to apply a plurality of impregnating steps, theimpregnating solutions to be used containing one or more of thecomponent precursors that are to be deposited, or a portion thereof(sequential impregnation). Instead of impregnating techniques, there canbe used dipping methods, spraying methods, and so forth. When carryingout multiple impregnation, dipping, etc., steps, drying may be carriedout between impregnation steps. However, a single impregnation step ispreferred because it is a faster, simpler process, allowing for a higherproduction rate, and is less costly. Single impregnation also tends toprovide catalysts of better quality.

When the at least one phosphorus compound, at least one Group VI metalcompound, and at least one Group VIII metal compound form part of themonomer-containing mixture, polymerization of the monomer species ispreferably performed after the impregnation step, althoughpolymerization can be started during impregnation of the carrier. Ifpolymerization is carried out after impregnation, polymerization can beperformed before or during removal of excess solvent if excess solventremoval is performed; preferably, polymerization is performed duringremoval of excess solvent. Similarly, when an impregnation solution anda carrier are brought together to form an impregnated carrier which isthen mixed with a monomer, polymerization is preferably performed duringremoval of excess solvent, if excess solvent removal is performed.

In the processes of this invention, polymerization is carried out in theusual manner, by exposing the monomer species to an initiator in anamount suitable to polymerize at least a portion of the monomer. Whenpresent, any inhibitor needs to be inactivated when starting thepolymerization reaction.

When at least one phosphorus compound, at least one Group VI metalcompound, and at least one Group VIII metal compound do not form part ofthe monomer-containing mixture, polymerization is initiated in thepresence of the carrier before impregnation, and an impregnationsolution is combined with the monomer-containing mixture duringpolymerization or after polymerization has ended.

Examples of polymers formed as part of the catalysts of the inventioninclude, but are not limited to, polyacrylic acid, polymaleic acid,polyfumaric acid, polycrotonic acid, poly(pentenoic) acid,polymethacrylic acid, polydimethacrylic acid, poly(allyl alcohol),poly(2-sulfoethyl)methacrylate, poly(n-propyl)acrylate,poly(hydroxymethyl)acrylate, poly(2-hydroxyethyl)acrylate,poly(2-carboxyethyl)acrylate, poly(3-ethoxy-3-oxopropyl)acrylate,poly(methylcarbamylethyl)acrylate, poly(2-hydroxyethyl)methacrylate,polyvinylpyrrolidone, polyacrylamide, polymethacrylamide,poly(N-isopropyl)acrylamide, polyvinylacetamide,polyvinyl-N-methylacetamide, poly(N-hydroxymethyl)acrylamide,poly(N-hydroxyethyl)acrylamide, poly(N-methoxymethyl)acrylamide,poly(N-ethoxymethyl)acrylamide, polyvinyl sulfate, polyvinyl sulfonicacid, poly(2-propyl)-1-sulfonic acid, polyvinyl phosphate, polyvinylphosphonic acid, poly(dimethyl allyl phosphate), poly(diethyl allylphosphate), polyvinyl phosphonic acid, and the like. As noted above,mixtures of two or more monomer species can be employed, and will formco-polymers.

Although the monomers used to form the supported catalyst will often besoluble in a polar solvent such as water, the polymer formed from themonomer(s) does not need to be soluble in water or other polar solvents.

The processes of the present invention yield supported catalysts inwhich the Group VIII metal is usually present in an amount of about 1 toabout 10 wt %, preferably about 3 to about 8.5 wt %, calculated as amonoxide. In these catalysts, phosphorus is usually present in an amountof about 0.5 to about 10 wt %, more preferably about 1 to about 9 wt %,calculated as P₂O₅. When the Group VI metal in the catalyst ismolybdenum, it will usually be present in an amount of about 35 wt % orless, preferably in an amount of about 15 to about 35 wt %, calculatedas molybdenum trioxide.

When at least one phosphorus compound, at least one Group VI metalcompound, and at least one Group VIII metal compound, or an impregnationsolution are included before or during polymerization, a supportedcatalyst is obtained at the end of the polymerization step. If instead apolymerized product is formed and then contacted with an impregnationsolution after polymerization, a supported catalyst is obtained at theend of the impregnation step or steps.

Optionally, excess solvent is removed from the supported catalyst.Removal of excess solvent may be carried out in air, under vacuum, or inthe presence of an inert gas. Solvent removal is preferably achieved bydrying the supported catalyst. Drying of the supported catalyst isconducted under such conditions that at least a portion of the polymerremains in the catalyst, i.e., the polymer is not completely removed bydecomposition. Thus, the drying conditions to be applied depend on thetemperature at which the particular polymer decomposes; decompositioncan include combustion when the drying is conducted in the presence ofoxygen. In these processes of the invention, drying should be carriedout under such conditions that about 50% or more, preferably about 70%or more, more preferably about 90% or more, of the polymer is stillpresent in the catalyst after drying. It is preferred to keep as much ofthe polymer as possible in the supported catalyst during drying;however, it is understood that loss of some of the polymer during thedrying step cannot always be avoided, at least for more easilydecomposed polymers. A drying temperature below about 270° C. may benecessary, depending on the polymer.

As mentioned above, the supported catalysts of this invention comprise acarrier, phosphorus, at least one Group VI metal, at least one GroupVIII metal, and a polymer, where the molar ratio of phosphorus to GroupVI metal is about 1:1.5 to less than about 1:12, the molar ratio of theGroup VI metal to the Group VIII metal is about 1:1 to about 5:1, andthe polymer has a carbon backbone and comprises functional groups havingat least one heteroatom. The carriers and the preferences therefor areas described above. The carrier in the supported catalysts of thisinvention is in an amount of about 40 wt % to about 80 wt %, preferablyabout 50 wt % to about 70 wt %, and more preferably about 60 wt % toabout 70 wt %, relative to the total weight of the carrier,hydrogenation metals, and phosphorus, where the hydrogenation metals andphosphorus are expressed as their oxides, i.e., excluding the polymer.The hydrogenation metals and the preferences therefor are as describedabove. In the polymers, the carbon backbone is sometimes referred to asa carbon-carbon backbone, where the backbone is the main chain of thepolymer. Polymers in the supported catalysts and the preferencestherefor are as described above.

Optionally, catalysts of the invention may be subjected to a sulfidationstep (treatment) to convert the metal components to their sulfides. Inthe context of the present specification, the phrases “sulfiding step”and “sulfidation step” are meant to include any process step in which asulfur-containing compound is added to the catalyst composition and inwhich at least a portion of the hydrogenation metal components presentin the catalyst is converted into the sulfidic form, either directly orafter an activation treatment with hydrogen. Suitable sulfidationprocesses are known in the art. The sulfidation step can take place exsitu to the reactor in which the catalyst is to be used in hydrotreatinghydrocarbon feeds, in situ, or in a combination of ex situ and in situto the reactor.

Ex situ sulfidation processes take place outside the reactor in whichthe catalyst is to be used in hydrotreating hydrocarbon feeds. In such aprocess, the catalyst is contacted with a sulfur compound, e.g., anorganic or inorganic polysulfide or elemental sulfur, outside thereactor and, if necessary, dried, preferably in an inert atmosphere. Ina second step, the material is treated with hydrogen gas at elevatedtemperature in the reactor, optionally in the presence of a feed, toactivate the catalyst, i.e., to bring the catalyst into the sulfidedstate.

In situ sulfidation processes take place in the reactor in which thecatalyst is to be used in hydrotreating hydrocarbon feeds. Here, thecatalyst is contacted in the reactor at elevated temperature with ahydrogen gas stream mixed with a sulphiding agent, such as hydrogensulfide or a compound which under the prevailing conditions isdecomposable into hydrogen sulphide (e.g., dimethyl disulfide). It isalso possible to use a hydrogen gas stream combined with a hydrocarbonfeed comprising a sulfur compound which under the prevailing conditionsis decomposable into hydrogen sulfide. In the latter case, it ispossible to sulfide the catalyst by contacting it with a hydrocarbonfeed comprising an added sulfiding agent such as dimethyl disulfide(spiked hydrocarbon feed), and it is also possible to use asulfur-containing hydrocarbon feed without any added sulfiding agent,since the sulfur components present in the feed will be converted intohydrogen sulfide in the presence of the catalyst. Combinations of thevarious sulfiding techniques may also be applied. The use of a spikedhydrocarbon feed may be preferred.

When the catalyst is subjected to an in situ sulfidation step, thecatalyst is exposed to high temperatures in the presence of oil andwater formed during the process before sulfidation is complete. Thisexposure to high temperatures in the presence of oil and water does notappear to adversely affect catalyst activity. Without wishing to bebound by theory, it is thought that the polymer is more resistant toleaching or evaporation in comparison to catalysts described in the artthat have low molecular weight organic additives.

The catalyst compositions of this invention are those produced by theabove-described process, whether or not the process included an optionalsulfiding step.

Without wishing to be bound by theory, both the observed greaterdispersion of the hydrogenation metals and weak (low) metal-supportinteraction are achieved by employing monomers having functional groupsas described above to form polymers in the supported catalysts. Suchpolymers are hypothesized to help disperse the hydrogenation metalsthroughout the pore network. Also without wishing to be bound by theory,hydrogenation metals are believed to interact with the polymer, whichdisperses the hydrogenation metals in the pore spaces of the support. Itis also hypothesized that activation of the catalyst in a sulfidingatmosphere replaces at least some of the polymer's functional groupheteroatoms with sulfur, which is believed to help minimize or preventthe hydrogenation metals from clustering together or interacting withthe support, which minimized clustering and/or interacting with thesupport in turn is believed to contribute to the observed enhancedcatalyst activity. In addition, it is theorized that the polymer (aftersulfidation) may suppress sintering of the hydrogenation metals,contributing to improved stability of the supported catalyst.

The catalyst compositions of this invention can be used in thehydrotreating, hydrodenitrogenation, and/or hydrodesulfurization of awide range of hydrocarbon feeds. Examples of suitable feeds includemiddle distillates, kero, naphtha, vacuum gas oils, heavy gas oils, andthe like.

Methods of the invention are methods for hydrotreating,hydrodenitrogenation, and/or hydrodesulfurization of a hydrocarbon feed,which methods comprise contacting a hydrocarbon feed and a catalyst ofthe invention. Hydrotreating of hydrocarbon feeds involves treating thefeed with hydrogen in the presence of a catalyst composition of theinvention at hydrotreating conditions.

Conventional hydrotreating process conditions, such as temperatures inthe range of about 250° to about 450° C., reactor inlet hydrogen partialpressures in the range of about 5 to about 250 bar (about 5×10⁵ Pa toabout 2.5×10⁷ Pa), space velocities in the range of about 0.1 to about10 vol./vol.hr, and Hz/feed ratios in the range of about 50 to about2000 NL/L, can be applied.

As shown in the Examples, polymer loadings up to at least 18 wt %relative to the other catalyst components were achieved. The amount ofpolymer present in the supported catalyst (polymer loading) is definedsimilarly to the way the amount of monomer relative to the othercatalyst components is defined above. In other words, the amount ofpolymer in the catalysts of this invention is expressed as wt % relativeto the total weight of the other components used to form the catalystexcluding any polar solvent. For example, if the total weight of theother components of the catalyst is 100 grams, 10 wt % of polymer is 10grams. In this invention, the polymer loading is generally about 1.5 wt% or more, preferably in the range of about 1.5 wt % to about 35 wt %,relative to the total weight of the other components in the catalyst,expressed as their oxides and excluding any polar solvent, althoughamounts outside these ranges are within the scope of the invention. Whenthe polymer is polyacrylic acid, the amount of polymer is morepreferably in the range of about 3 wt % to about 27 wt %, and even morepreferably in the range of about 5 wt % to about 20 wt % relative to thetotal weight of the other components of the catalyst.

The following examples are presented for purposes of illustration, andare not intended to impose limitations on the scope of this invention.

In several Examples below, a carbon yield (C-yield) is reported. Thecarbon yield is defined as the % of carbon that was introduced into thesample via the monomer and was still present after drying of thematerials.

In Tables 3, 5, 8, and 9 below, the catalyst activities are reported asthe rate constants k_(wt,HDS) and k_(wt,HDN). For sulfur, the rateconstant k_(wt,HDS) was calculated using the following formula:

k _(wt,HDS)=WHSV*1/(n−1)*(1/S ^(n−1)−1/S ₀ ⁻¹)

where WHSV is the weight hourly space velocity (g_(oil)/g_(cat)/h); S isthe percentage of sulfur in the product (ppm wt S); S₀ is the percentageof sulfur in the feed (ppm wt S); and n is the reaction order of thehydrodesulfurisation reaction. For tests at 20 bar (2.0×10⁶ Pa) and 45bar (4.5×10⁶ Pa), an n value of 1.4 was used. For testing at 90 bar(9.0×10⁶ Pa), an n value of 1.2 was used.

For nitrogen, the rate constant k_(wt,HDN) was calculated using thefollowing formula:

k _(wt,HDN)=WHSV*ln(N ₀ /N)

where WHSV is the weight hourly space velocity (g_(oil)/g_(cat)/h); N isthe percentage of nitrogen in the product (ppm wt N); and No is thepercentage of nitrogen in the feed (ppm wt N). The WHSV was calculatedbased on the catalyst weight after calcination in air at 600° C.

Example 1—Comparative

Polymerization of Monomer without Hydrogenation Metals

A solution was made by dissolving acrylic acid (AA; 1.8 g) in water (40g). Ammonium persulfate (or peroxydisulfate, APS; 0.6 g) dissolved inwater (2 g) was added to the solution. To start the polymerizationreaction, the solution was heated to 70° C. with vigorous stirring. Uponreaching 70° C., the viscosity noticeably increased, and a clear gel wasformed. The resulting gel was dried overnight at 120° C., yielding awhite-yellow polymer film.

For Examples 2 and 3, a stock impregnation solution containing 90 g/Lcobalt as CoO, 491 g/L molybdenum as MoO₃, and 37 g/L phosphorus as P₂O₅was prepared by mixing together cobalt carbonate (Co(OH)_(X)(CO₃)_(Y)),MoO₃, H₃PO₄ (aq., 85%), and water in appropriate amounts. The mixturewas heated at temperatures above 70° C. until a clear solution wasobtained. No monomer was present in this stock solution.

Example 2—Comparative Polymerization of Monomer in Presence ofHydrogenation Metals

AA (1.58 g) was dissolved in 15 grams of the above stock solution withvigorous stirring. APS (0.35 g) dissolved in water (0.53 g) was thenadded to the solution. To initiate the polymerization reaction, thesolution was heated to 70° C. with vigorous stirring. Upon reaching 70°C., the viscosity noticeably increased. Upon cooling, a rubbery mass wasformed. The rubbery mass was dried overnight at 120° C., yielding aporous, brittle residue.

Example 3 Preparation of Polymer-Modified Catalyst Containing Co and Mo

A series of samples was made with varying quantities of acrylic acid(AA) in portions of the above-described stock solution. The quantity ofammonium persulfate (APS) was held constant in these samples. Theamounts of the reagents are listed in Table 1; Run C1 is comparative,containing an initiator but no monomer. A quantity of the above stocksolution was weighed into a round bottom flask. Acrylic acid was added,and the contents were mixed by swirling the flask. Ammonium persulfate(APS) was then added, and the contents were mixed by swirling the flask.

Extrudates of gamma-alumina having a surface area of 253 m²/g were addedto the solution for incipient wetness impregnation, and the contentswere mixed by swirling the flask. The round bottom flask was placed on arotary evaporator for 90 minutes with gentle rotation at roomtemperature. The temperature of the water bath was then raised to 80° C.to start the polymerization reaction (temperature was reached in 10min.), and then the mixture was kept at 80° C. for 60 minutes; duringthis step, the system was closed to prevent evaporation. Then thepolymer-modified impregnated extrudates obtained were transferred to apan, dried with cold air, and then with hot air, to a producttemperature of about 90° C.

The carbon content of the resulting catalysts was measured using totalcarbon analysis, and the carbon yields in grams and as percentage of themonomer carbon content are shown in Table 1.

TABLE 1 Run 1 2 3 4 C1 Alumina 50.00 g  50.00 g  50.00 g  50.00 g  50.00g  Stock soln. 52.95 g  52.95 g  52.95 g  52.95 g  52.95 g  AA 1.81 g3.60 g 5.40 g 7.20 g 0.00 APS 0.15 g 0.15 g 0.15 g 0.15 g 0.15 g H₂O5.40 g 3.60 g 1.80 g 0 7.20 g Carbon 0.90 g 1.53 g 2.28 g 3.06 g N/AC-yield 100% 85% 85% 85% N/A

Example 4 Activity Testing of Catalysts Containing Co and Mo

The catalysts formed in Example 3 were ground; powder fractions of 125to 350 μm were isolated by sieving. The 125 to 350 μm fractions wereevaluated for their performance in hydrodesulfurization andhydrodenitrogenation. The catalysts were sulfided by contacting themwith dimethyl disulfide (2.5 wt % S) spiked straight run gas oil (SRGO)in a two-step process with a temperature hold for 8 hours at 250° C. and5 hours at 320° C. and 20 bar (2.0×10⁶ Pa) just prior to running thetest.

The boiling point distribution of two straight run gas oil feeds, Feed Aand Feed B, are shown in Table 2. Feed A contained 1.1678 wt % sulfur,94.4 ppm of nitrogen, and had a density of 0.8366 g/mL.

TABLE 2 Feed A Feed B Feed C Initial boiling 167° C. 142° C. 160° C.point 10 wt % 205° C. 197° C. 245° C. 20 wt % 217° C. 212° C. 262° C. 30wt % 241° C. 235° C. 276° C. 40 wt % 256° C. 250° C. 292° C. 50 wt %269° C. 265° C. 306° C. 60 wt % 281° C. 278° C. 321° C. 70 wt % 294° C.291° C. 338° C. 80 wt % 307° C. 307° C. 358° C. 90 wt % 323° C. 325° C.382° C. Final boiling 347° C. 347° C. 426° C. point

The samples were then tested for their performance inhydrodesulfurization and hydrodenitrogenation with straight run gas oil(SRGO) of Feed A. The samples were tested at 20 bar; the temperature was345° C., the H₂ to oil ratio was 300 NL/L, and the weight hourly spacevelocity (WHSV) was in the range of 1.31 to 1.42/hour (g_(oil)/geat/h).The actual weight of catalyst in the different reactors, the appliedWHSV, and the sulfur and nitrogen values in the liquid product samplesare presented for the different catalysts in Table 3. Sulfur andnitrogen values were obtained by taking the average value of liquidproduct samples obtained between 1 and 9 days after introduction of FeedA. The HDS order used was 1.4.

Results are summarized in Table 3, which shows activity results of theseruns using catalysts made according to Example 3 relative to comparativecatalyst C1. The comparative catalyst contained cobalt, molybdenum, andphosphorus in amounts similar to the inventive catalysts tested, and thecomparative catalyst was prepared in the presence of ammonium persulfate(initiator), but without a monomer present. As Table 3 shows, thehydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activityincreased up to about 14% as the amount of polyacrylic acid increasedfrom 0% to about 8 wt %.

TABLE 3 Polymer Test result Activity loading* WHSV S N k_(wt, HDS)k_(wt, HDN) Run wt % g_(oil)/g_(cat)/h ppm ppm n = 1.4 n = 1 1 2.4 1.3964.6 35.6 0.65 1.35 2 4.1 1.31 48.8 31.3 0.69 1.45 3 6.1 1.42 57.8 34.10.70 1.45 4 8.2 1.42 50.1 32.8 0.74 1.50 C1 0 1.39 65.9 36.5 0.65 1.32*Relative to the total weight of other components in the catalyst,excluding any polar solvent, and using observed carbon yield.

Example 5 Preparation of Polymer-Modified Catalyst Containing Ni and Mo

A stock impregnation solution containing 100 g/L nickel as NiO, 599 g/Lmolybdenum as MoO₃, and 42 g/L phosphorus as P₂O₅ was prepared by mixingtogether nickel carbonate (Ni(OH)_(X)(CO₃)_(Y)), MoO₃, H₃PO₄ (aq., 85%),and water in appropriate amounts. The mixture was heated at temperaturesabove 70° C. until a clear solution was obtained. No monomer was presentin this stock solution.

The procedure of Example 3 was followed to prepare catalyst samplescontaining Ni, Mo, and P with acrylic acid, using the just-describedstock solution, and an extruded alumina carrier having a surface area ofeither 205 m²/g or 271 m²/g. When ammonium persulfate (APS) was used asthe initiator, a yellow deposit was formed. APS was replaced withpotassium persulfate (KPS) by adding the same molar amount as APS. Theamounts of the reagents are listed in Table 4; Runs C2 and C3 arecomparative and contained the initiator but no monomer. The carboncontent of the resulting catalysts was measured using total carbonanalysis, and the carbon yields in grams and as percentage of themonomer carbon content are shown in Table 4.

TABLE 4 Run C2 A B C C3 Alumina 53.19 g 53.19 g 50.41 g 50.41 g 50.41 gSurface 271 271 205 205 205 area m²/g m²/g m²/g m²/g m²/g Stock 45.93 g45.93 g 45.93 g 45.93 g 45.93 g soln. AA    0 g  7.8 g  7.8 g  15.6 g   0 g KPS  0.18 g  0.18 g  0.18 g  0.18 g  0.18 g H₂O  15.6 g  7.8 g 8.06 g    0 g 15.86 g Carbon N/A  3.20 g  3.19 g  6.86 g N/A C-yieldN/A 82% 82% 88% N/A

Raman spectra of the catalysts prepared in Examples 3 and 5 show clearevidence that polymerization has occurred. The Raman measurements wereperformed at 532 nm excitation; the laser power was controlled to avoidsample damage. The spectra were recorded with a 10×30 second acquisitiontime. FIG. 1 shows a typical Raman spectrum obtained from catalyst B ofExample 5 (Table 4). The spectrum shows an intense band around 2933cm⁻¹, typical for polyacrylic acid. The bands at lower intensity around3040 cm⁻¹ and 3110 cm⁻¹ are caused by the ν(CH) and ν(CH₂)_(asy)vibrations, respectively, of the acrylic acid monomer. The highintensity of the 2933 cm⁻¹ peak relative to the 3040 cm-1 and 3110 cm⁻¹peaks clearly indicates that polymerization of the acrylic acid hastaken place in this catalyst. For a validation of the assignments ofdifferent peaks, see for example, C. Murli and Y. Song, Journal ofPhysical Chemistry B, 2010, 114, 9744-9750.

Example 6 Activity Testing of Catalysts Containing Ni and Mo

There is a clear activity advantage for catalysts prepared with acrylicacid versus samples without any monomer (polymer). In this Example,activity testing of the catalysts prepared in Example 5 was carried outas described in Example 4, except that a different test feed was used,and the reactors were operated at 90 bar (9.0×10⁶ Pa) rather than 20bar. The test feed was Feed B, which consisted of 50% light cycle oil(LCO) and 50% straight run gas oil (SRGO), and contained 1.1317 wt %sulfur, 277 ppm of nitrogen, and had a density of 0.8750 g/mL; theboiling point distribution of Feed B is in Table 2. The temperature was308° C. for the HDN and 315° C. for the HDN test; the H₂ to oil ratiowas 400 NL/L, and the weight hourly space velocity (WHSV) was in therange of 1.66-2.04/hour for the HDN test and 1.14-1.22/hour for the HDStest. The actual weight of catalyst in the different reactors, theapplied WHSV, and sulfur and nitrogen values in the liquid productsamples are presented for the different catalysts in Table 5. Sulfur andnitrogen values were obtained by taking the average value of liquidproduct samples obtained between 1 and 11 days after introduction ofFeed B for the HDN test and between 14 and 22 days after introduction ofFeed B for the HDS test. HDS data for comparative catalyst C3 were notgenerated due to a premature reactor shutdown. The HDS order used was1.3.

Results are summarized in Table 5, which shows activity results for thecatalysts made in this Example in comparison to the appropriatecomparative catalyst. The hydrodesulfurization (HDS) activity andhydrodenitrogenation (HDN) activity increased up to about 20% as theamount of polyacrylic acid in the catalyst increased from 0% up to about19 wt %.

TABLE 5 Polymer Test result Activity Carrier loading* WHSV_(HDN)WHSV_(HDN) S N k_(wt, HDS) k_(wt, HDN) Run surf. area wt %g_(oil)/g_(cat)/h g_(oil)/g_(cat)/h ppm ppm n = 1.4 n = 1 C2 271 m²/g 01.14 1.97 307 25.6 0.68 4.7 A 271 m²/g 8.3 1.22 1.98 324 18.3 0.72 5.4 B205 m²/g 8.6 1.19 2.04 255 23.0 0.75 5.1 C 205 m²/g 18.6 1.15 1.95 17315.5 0.82 5.6 C3 205 m²/g 0 N/A 1.66 N/A 20.4 N/A 4.3 *Relative to thetotal weight of other components in the catalyst, excluding any polarsolvent, and using observed carbon yield.

Example 7—Comparative Polymerization of Various Monomers withoutHydrogenation Metals Present

Several solutions, each with a different monomer and potassiumpersulfate (KPS) were prepared in water. The monomers, and the amountsof monomer, KPS, and water are listed in Table 6. Clear solutions wereobtained by mixing all of the components at room temperature.Subsequently, each solution was heated in a closed vessel at 80° C. Thechange in appearance of each solution at elevated temperature was usedto judge whether polymerization had occurred. Based on theseobservations, polymerization had occurred for all of the monomers testedexcept for ethylene glycol vinyl ether.

TABLE 6 Amt. Amt. Amt. Observation Monomer monomer water KPS (above 50°C.) Acrylic acid 7.5 g 22.2 g 0.06 g at 57° C. transparent gel2-Carboxyethyl 7.5 g 22.7 g 0.06 g at 75° C. gel; precipitation acrylateat cool down Maleic acid 7.1 g 24.8 g 0.05 g precipitation at cool downN-Hydroxyethyl 7.5 g 22.7 g 0.06 g at 55° C. yellow gel acrylamideEthylene glycol 7.5 g 21.8 g 0.06 g no change vinyl ether

Example 8 Polymerization of various monomers in the presence of an Al₂O₃carrier

Several aqueous solutions, each with a different monomer, potassiumpersulfate and extrudates of Al₂O₃ (surface area, BET: 266 g/m²), wereprepared at a concentration of 0.24 g monomer/g Al₂O₃ and 0.012 gK₂S₂O₈/g Al₂O₃. The monomers are listed in Table 7. The resultingextrudates saturated with the aqueous monomer solutions were heated for16 hours at 80° C. in a closed vessel. Next, the samples were kept at120° C. in an open vessel for 1 hour to remove excess water. The carboncontent of the thus obtained materials are reported in Table 7.

A support loaded with ethylene glycol vinyl ether, which does notpolymerize in water (see Example 7) was prepared for comparison usingthe same preparation method. From the wt % carbon and C-yield forcomparative run C4, it is clear that a significant amount of ethyleneglycol vinyl ether was released upon heat treatment at 120° C. Thisshows that no or very incomplete polymerization occurred for ethyleneglycol vinyl ether, and that this monomer had mostly evaporated duringdrying at 120° C.

TABLE 7 Carrier Monomer Carbon C-yield D Acrylic acid 9.53 wt % 100% E2-Carboxyethyl acrylate 8.17 wt % 100% F Maleic acid 7.08 wt % 100% GN-Hydroxyethyl acrylamide 9.77 wt % 100% C4 Ethylene glycol vinyl ether2.79 wt %  29%

Example 9 Raman Measurements of Different Monomers on Al₂O₃ Supports

A carrier sample was prepared for comparative purposes. An extrudedAl₂O₃ carrier as in Example 8 was saturated with an aqueous solution ofacrylic acid at a concentration of 0.24 g monomer/g Al₂O₃ without KPSpresent. The extrudates, saturated with the aqueous monomer solution,were heated for 16 hours at 80° C. in a closed vessel. Next, theextrudates were kept at 120° C. in an open vessel for 1 hour to removeexcess water. This was comparative sample C5.

Raman spectra were recorded for comparative sample C5, and for Carrier Dand Carrier F from Example 8 (Table 7); the Raman spectra are shown inFIG. 2 . The Raman measurements were performed at 514 nm excitation; thelaser power was controlled to avoid sample damage. The spectra wererecorded with a 10×10 second acquisition time.

The spectrum of comparative sample C5 shows peaks characteristic ofunreacted acrylic acid. The peak at 1640 cm⁻¹, which is associated withC═C stretch vibrations, is a clear sign that unreacted acrylic acid waspresent in comparative sample C5. The spectrum of Carrier D clearlyshows that polymerization had occurred; the peak at 2929 cm⁻¹ ischaracteristic for polyacrylic acid. The absence of a peak at 1640 cm⁻¹indicated that no C═C bonds were present in Carrier D. For a validationof the assignments of peaks characteristic of acrylic acid andpolyacrylic acid, see for example, C. Murli and Y. Song, Journal ofPhysical Chemistry B, 2010, 114, 9744-9750. The spectrum of Carrier Fshows bands that can be assigned to unreacted maleic acid and topolymaleic acid. The peak at 2931 cm⁻¹ indicates that a significantamount of polymaleic acid was present, while the peaks at 1657 cm⁻¹ and3052 cm⁻¹ indicate the presence of unreacted C═C bonds in Carrier F. Fora validation of the assignments of peaks characteristic of maleic acidand polymaleic acid, see for example, C. Q. Yang and X. Gu, Journal ofApplied Polymer Science, 2001, 81, 223-228. Thus Carriers D and F, eachof which had an initiator, contained a significant amount of polymer,while sample C5, which did not have an initiator, did not containdetectable amounts of polymer.

These experiments show that an appropriate initiator and/or conditionsappear to be needed to polymerize monomers in the presence of carriers.In other words, the carrier by itself does not induce polymerization ofthe monomer(s).

Example 10 Preparation of Polymer-Modified Catalyst Containing Co and Mo

The materials prepared in Example 8 were loaded with metals by porevolume impregnation. A stock solution containing Mo at a concentrationof 583 g MoO₃/L, Co at a concentration of 104 g CoO/L and H₃PO₄ at aconcentration of 42 g P₂O₅/L was prepared by mixing MoO₃,Co(OH)_(X)(CO₃)_(Y), and H₃PO₄ (aq., 85%), and water in appropriateamounts, and agitating and heating this mixture at 70° C. or above untila clear solution was obtained. As an additional comparative sample, thesame stock solution and preparation method were used to prepare acatalyst starting from Al₂O₃ extrudates like those used in Example 8,but without any monomer. For each preparation, the stock solution wasdiluted with enough water so that the final catalyst samples eachcontained 28 wt % MoO₃, measured after calcination at 600° C.

Example 11 Activity Testing of Catalysts Containing Co and Mo

The catalysts prepared as described in Example 10 were ground; powderfractions of 125 to 350 μm were isolated by sieving. The 125 to 350 μmfractions were evaluated for their performance in hydrodesulfurizationand hydrodenitrogenation. The catalysts were sulfided by contacting themwith dimethyl disulfide (2.5 wt % S) spiked SR-LGO in a two-step processwith a temperature hold for 8 hours at 250° C. and 5 hours at 320° C.just prior to running the test. The samples were tested at 45 bar(4.5×10⁶ Pa) for their performance in hydrodesulfurization andhydrodenitrogenation with straight run gas oil (SRGO) of Feed B. Feed Bcontained 7914 ppm sulfur, 169 ppm of nitrogen, and had a density of0.8574 g/mL; the boiling point distribution of Feed B is shown in Table2. Catalyst activity was evaluated at a temperature of 350° C., whilethe H₂ to oil ratio was 300 NL/L, and the weight hourly space velocity(WHSV) was in the range of 2.5-3.5/hour. The actual weight of catalystin the different reactors, the applied WHSV, and sulfur and nitrogenvalues in the liquid product samples are presented for the differentcatalysts in Table 8. S and N values were obtained by taking the averagevalue of 4 liquid product samples obtained between 6 and 8 days afterintroduction of Feed B. The HDS order used was 1.4.

TABLE 8 Test result Activity WHSV S N k_(wt, HDS) k_(wt, HDN) RunCarrier* Monomer g_(oil)/g_(cat)/h ppm ppm n = 1.4 n = 1.0 H D Acrylicacid 3.10 31.1 6.5 1.75 10.1 I E 2-Carboxyethyl acrylate 2.85 18.1 3.82.04 10.8 J F Maleic acid 2.63 15.1 3.1 2.04 10.5 K G N-Hydroxyethylacrylamide 2.71 15.8 3.0 2.06 10.9 C6 C4 Ethylene glycol vinyl ether2.57 28.4 7.2 1.51 8.1 C7 Al₂O₃ None 2.74 50.6 24.6 1.24 5.3 *SeeExample 8 and Table 7.

There is a clear benefit in the HDS and HDN activity of catalysts H—K ascompared to catalyst C7, to which no monomer was added, and catalyst C6,for which polymerization did not take place on the support. The resultsin the above Table show that introduction of a monomer to the carrierbefore introduction of the active metals is feasible, and thatpolymerization of the monomer provides the catalyst activity benefit.

Example 12—Comparative

A commercially applied CoMo/Al₂O₃ hydroprocessing catalyst having 24 wt% Mo as MoO₃, 4 wt % Co as CoO, and 2 wt % P as P₂O₅ was calcined toremove coke and convert the sulfides into oxides. The calcinationtemperature was high enough to remove all of the coke, but low enough toprevent substantial formation of bulk phases and CoAl₂O₄. Thisregenerated CoMo/Al₂O₃ catalyst was sample C8. To form sample C9, someof sample C8 was contacted with an aqueous solution of maleic acid. Theaqueous maleic acid solution was applied via pore volume impregnation ata concentration of 0.10 g maleic acid per g catalyst. Afterimpregnation, the material was left to stand for 3 hours at 50° C. in aclosed vessel and afterwards heated to 120° C. in air to remove water.This maleic acid-contacted catalyst was sample C9. A Raman spectrum ofsample C9 did not show peaks characteristic of polymaleic acid.

Example 13—Comparative Activity Testing of Catalysts Containing Co andMo without Polymer

Catalysts as described in Example 12 (samples C8 and C9) were ground;powder fractions of 125 to 350 μm were isolated by sieving. The 125 to350 μm fractions were evaluated for their performance inhydrodesulfurization. The catalysts were sulfided by contacting themwith dimethyl disulfide (2.5 wt % S) spiked SR-LGO in a two-step processwith a temperature hold for 8 hours at 250° C. and 5 hours at 320° C.just prior to running the test. The samples were tested at 45 bar(4.5×10⁶ Pa) for their performance in hydrodesulfurization with straightrun gas oil (SRGO) of Feed C. Feed C contained 7914 ppm sulfur, 169 ppmof nitrogen, and had a density of 0.8574 g/mL; the boiling pointdistribution of Feed C is shown in Table 2. Catalyst activity wasevaluated at a temperature of 350° C., while the H₂ to oil ratio was 300NL/L, and the weight hourly space velocity (WHSV) was in the range of2.5-3.5/hour. The actual weight of catalyst in the different reactors,the applied WHSV, and sulfur values in the liquid product samples arepresented for the different catalysts in Table 9. S values were obtainedby taking the average value of 4 liquid product samples obtained between6 and 8 days after introduction of the SRGO. The HDS reaction order usedwas 1.4.

TABLE 9 Test result Activity WHSV S K_(wt, HDS) Run Monomerg_(oil)/g_(cat)/h ppm n = 1.4 C8 none 3.15 101 1.03 C9 Maleic acid 3.27107 1.04

Comparison of the results in Table 9 with those of Run J in Table 8demonstrates two points. The first point demonstrated is that ahydroprocessing catalyst by itself (without a polymerization initiator)does not induce polymerization of a monomer species in the presence ofthe catalyst. The second point demonstrated is that the presence of anunpolymerized monomer does not appreciably increase the activity of thecatalyst. Thus, an appropriate initiator and/or conditions are needed toensure that polymerization of the monomer can take place.

EXAMPLES 14-15

The catalysts in Examples 14 and 15 were prepared in a manner similar tothat described in Example 3 of the Specification: an impregnationsolution containing cobalt, molybdenum, and phosphorus was prepared bymixing together cobalt carbonate (Co(OH)_(X)(CO₃)_(Y)), MoO₃, H₃PO₄(aq., 85%), and water in appropriate amounts. The mixture was heated attemperatures above 70° C. until a clear solution was obtained. Noacrylic acid monomer was present in this solution. The solution wasadded to a quadrilobed-shaped alumina support via pore volumeimpregnation, and the resulting catalyst was subsequently dried. Thecatalysts contained 23.7 wt % MoO₃, 4.6 wt % CoO, and 2.0 wt % P₂O₅ onAl₂O₃. A portion of the catalyst was used in of the impregnationexperiments in Examples 14 and 15.

Example 14

In this experiment, an aqueous solution containing acrylic acid andpotassium persulfate was mixed with a portion of the catalyst preparedabove. The flask containing the catalyst mixture was heated and dried asdescribed in Example 3 above. The final catalyst was a free-flowingpowder that was light brown in color.

Example 15—Comparative

An aqueous solution of polyacrylic acid was made and added to theCoMoP—Al₂O₃ catalyst. The polyacrylic acid had a molecular weight of1800, and was obtained commercially from Sigma Aldrich Company. Thetarget loading of polymer was 20 wt % with respect to the combinedweight of Al₂O₃+MoO₃+CoO+P₂O₅ (excluding water). For example, 5.55 gramsof catalyst with a water content of 10% corresponds to −5 grams ofcatalyst excluding water; the target polymer loading for such a catalystis 1 gram. The concentration of the aqueous solution containing 1 gramof polyacrylic acid was adjusted to result in a pore volumeimpregnation, i.e. to not overfill the pores. After addition of theaqueous polymer solution to the dry catalyst, the material was aged at40° C. for 2 hours to make the material homogeneous, and then thecatalyst was dried at 120° C. The final material was red in color, andthe catalyst particles appeared to be glued together.

Both the monomer impregnated catalyst of Example 14 and thepolymer-contacted catalyst of Example 15 were subjected to scanningelectron microscopy energy-dispersive x-ray spectroscopy (SEM-EDX) tomap the location of various elements in the catalyst particles. Thecatalysts were placed in a carbon matrix (embed resin) for these scans.Cross sections of the quadrilobed particles are shown in FIGS. 3-1 to3-5 .

In FIGS. 3-1 to 3-5 , side-by-side comparisons of the SEM-EDX resultsare shown; the A column is for the monomer-impregnated catalyst ofExample 14, and the B column is for the polymer-contacted catalyst ofExample 15. The quadrilobed shape of the catalyst particles can be seenin the images for both catalysts. The polymer-contacted catalyst showsseveral particles close together because they are stuck together, whilethe monomer-impregnated catalyst particle is separate from other suchparticles. Because the support material is Al₂O₃, the aluminum signal isquite strong (FIG. 3-1 ). The carbon signals (FIG. 3-2 ) are quitestrong around the particles because they are in a carbon matrix. Thecarbon cross section shows no signal from the monomer-impregnatedcatalyst particle (A) because the amount of carbon in the particle ismuch lower. The polymer-impregnated catalyst particles (B) show a lowercarbon signal between the particles, indicating that there is no carbonmatrix there, but instead something with a lower carbon concentration.

In FIG. 3-3 , the oxygen signal in the monomer-impregnated catalystparticle is contained in the catalyst particle, indicating that all ofthe polymer formed from the monomers is contained within the catalystparticle. The oxygen signal of the polymer-impregnated particle (B)shows the presence of oxygen between the particles, approximatelyco-extensive with the area of dimming seen in the carbon cross-sectionin FIG. 3-2 , indicating that polyacrylic acid is present outside of thecatalyst particles.

The molybdenum cross sections of the catalyst particles (FIG. 3-4 ) arefainter because the amount of molybdenum is low relative to the amountsof aluminum and oxygen, resulting in a lower signal-to-noise ratio. Thecobalt cross sections (FIG. 3-5 ) have an even lower signal-to-noiseratio than the molybdenum cross sections because the amount of cobalt islower than the amount of molybdenum. For the monomer-impregnatedcatalyst particle (A), the cobalt cross section is of the same shape asthe cross sections for aluminum and carbon. The polymer-impregnatedcatalyst particles (B) have a relatively uniform cobalt signal,indicating that some of the cobalt migrated (leached) out into thepolyacrylic acid that is outside of the catalyst particles. Thismigration of catalyst metals such as cobalt is generally undesirable,because homogenous distribution of the metals in the catalyst particleis preferred.

EXAMPLES 16-18

The catalysts in these runs were prepared using the one-stepimpregnation method described above, and polyacrylic acid was usedinstead of acrylic acid monomer to determine whether polyacrylic acidwith very low molecular weight could be incorporated into the porestructure of Al₂O₃. In all three Examples, the Al₂O₃ support had a porevolume of 0.80 mL/g.

Example 16—Comparative

A polyacrylic acid (PAA) solution was made which upon pore volumeimpregnation of the Al₂O₃ support would result in a polymerconcentration in the final catalyst of approximately 7 wt %. In 50 mLH₂O, 6.11 g of polyacrylic acid (mw 450; Sigma Aldrich) were dissolved(c_(PAA)=0.12 g/mL) by adding the PAA slowly while stirring at atemperature of 40 to 50° C. After all of the PAA had dissolved, aviscous solution with a pH of 1.9 was obtained. The pH was increased to5.3 by adding NaOH (which in effect resulted in the formation of Napolyacrylate). Upon addition of the NaOH, the solution became even moreviscous. It became clear that PAA solutions in water are highly viscouseven at low concentrations, regardless of the presence of sodium. Theviscous solution (gel) was brought into contact with the Al₂O₃, whichremained on top of the gel without any imbibition of the solution (gel)into the pores. As it became obvious that impregnation was not going tooccur, the experiment was halted and not all of the Al₂O₃ was added tothe solution (gel). Results are summarized in Table 13.

Example 17—Comparative

A PAA solution was made which upon pore volume impregnation of the Al₂O₃support would result in a polymer concentration in the final catalyst ofabout 1 wt %. In 50 mL of distilled water, 1.0 g of PAA (mw 1250, SigmaAldrich) was dissolved (c_(PAA)=0.02 g/mL) by adding the PAA whilestirring at a temperature of about 50° C.; the solution immediatelybecame viscous when PAA was added to the heated water. The solution(gel) was brought into contact with Al₂O₃, which remained on top of thegel without any imbibition of the solution (gel) into the pores. As itbecame obvious that impregnation was not going to occur, the experimentwas halted and not all Al₂O₃ was added to the solution (gel). Resultsare summarized in Table 13.

Example 18—Comparative

Acrylic acid monomer was used in this experiment, and the concentrationof acrylic acid, upon pore volume impregnation of the Al₂O₃ support,would result in a polymer concentration in the final catalyst ofapproximately 23 wt %, a much higher concentration than was used inExamples 16 and 17. In 50 mL of distilled water, 20.50 g acrylic acidand 0.50 g ammonium persulfate were dissolved (c_(AA)=0.41 g/mL). Theammonium persulfate was an initiator for the polymerization. Thissolution was not viscous. The monomer-containing solution was heated toa temperature of >80° C. to initiate the polymerization of acrylic acidto PAA. Upon polymerization, gel formation occurred rapidly, similar tothe PAA solutions (gels) obtained in Examples 16 and 17. Results aresummarized in Table 13.

TABLE 13 Expected amount Ex. T PAA mw PAA in catalyst Result 16 450  7wt % gel—no impregnation 17 1250  1 wt % gel—no impregnation 18 Beforepolym. 23 wt % soln.—impregnation possible After polym. 23 wt % gel—noimpregnation

In Examples 16-18, the impregnations were pore volume impregnation orincipient wetness impregnation, in which, as noted above, theimpregnation solution will be taken up virtually completely by the poresof the catalyst support. If impregnation had worked in Examples 16-18,all of the solution would have gone into the pores. The fact that thesolutions remained indicates that there was minimal or no uptake ofpolymer into the pores of the Al₂O₃ support.

Components referred to by chemical name or formula anywhere in thespecification or claims hereof, whether referred to in the singular orplural, are identified as they exist prior to coming into contact withanother substance referred to by chemical name or chemical type (e.g.,another component, a solvent, or etc.). It matters not what chemicalchanges, transformations and/or reactions, if any, take place in theresulting mixture or solution as such changes, transformations, and/orreactions are the natural result of bringing the specified componentstogether under the conditions called for pursuant to this disclosure.Thus the components are identified as ingredients to be brought togetherin connection with performing a desired operation or in forming adesired composition. Also, even though the claims hereinafter may referto substances, components and/or ingredients in the present tense(“comprises”, “is”, etc.), the reference is to the substance, componentor ingredient as it existed at the time just before it was firstcontacted, blended or mixed with one or more other substances,components and/or ingredients in accordance with the present disclosure.The fact that a substance, component or ingredient may have lost itsoriginal identity through a chemical reaction or transformation duringthe course of contacting, blending or mixing operations, if conducted inaccordance with this disclosure and with ordinary skill of a chemist, isthus of no practical concern.

The invention may comprise, consist, or consist essentially of thematerials and/or procedures recited herein.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term about alsoencompasses amounts that differ due to different equilibrium conditionsfor a composition resulting from a particular initial mixture. Whetheror not modified by the term “about”, the claims include equivalents tothe quantities.

Except as may be expressly otherwise indicated, the article “a” or “an”if and as used herein is not intended to limit, and should not beconstrued as limiting, the description or a claim to a single element towhich the article refers. Rather, the article “a” or “an” if and as usedherein is intended to cover one or more such elements, unless the textexpressly indicates otherwise.

Each and every patent or other publication or published documentreferred to in any portion of this specification is incorporated in totointo this disclosure by reference, as if fully set forth herein.

This invention is susceptible to considerable variation in its practice.Therefore the foregoing description is not intended to limit, and shouldnot be construed as limiting, the invention to the particularexemplifications presented hereinabove.

That which is claimed is:
 1. A supported catalyst comprising a carrier,phosphorus, at least one Group VIB metal, at least one Group VIII metal,and a polymer, where the molar ratio of phosphorus to Group VIB metal isabout 1:1.5 to less than about 1:12, the molar ratio of the Group VIBmetal to the Group VIII metal is about 1:1 to about 5:1, and the polymerhas a carbon backbone, comprises functional groups having at least oneheteroatom, wherein the polymer is formed by polymerizing a monomer incontact with the carrier, wherein the monomer and carrier are broughttogether, and wherein the polymer loading is about 1.5 wt % or more,relative to the total weight of the other components in the catalyst. 2.A catalyst as in claim 1 wherein said carrier is silica, alumina,silica-alumina, alumina with silica-alumina dispersed therein,alumina-coated silica, or silica-coated alumina, and/or wherein thefunctional groups of the polymer are carboxylic acid groups.
 3. Acatalyst as in claim 1 wherein the molar ratio of phosphorus to GroupVIB metal is about 1:2.5 to less than about 1:12.
 4. A catalyst as inclaim 1 wherein the polymer is polymaleic acid, polyfumaric acid, orpolyacrylic acid.
 5. A catalyst as in claim 1 wherein said Group VIBmetal is molybdenum and/or tungsten, and/or wherein said Group VIIImetal is nickel and/or cobalt.
 6. A catalyst as in claim 1 wherein thecarrier is about 40 wt % to about 80 wt % of the catalyst, relative tothe total weight of the carrier, the Group VI metal or metals and theGroup VIII metal or metals, and phosphorus, where the Group VI metal ormetals and the Group VIII metal or metals and phosphorus are expressedas their oxides.
 7. A method for hydrotreating, hydrodenitrogenation,and/or hydrodesulfurization, which method comprises contacting ahydrocarbon feed and a catalyst of claim
 1. 8. A catalyst as in claim 1wherein at least the phosphorus, Group VIB metal, and Group VIII metalare introduced to the carrier in a single impregnation step, and/orwherein the carrier has been calcined and/or extruded prior to contactwith the other catalyst components.
 9. A supported catalyst formed by aprocess comprising I) bringing together components in any of thefollowing combinations: a-i) a carrier, one or more monomer species, apolar solvent, and optionally an initiator, b-i) a carrier, one or moremonomer species, at least one phosphorus compound, at least one GroupVIB metal compound, and at least one Group VIII metal compound, andoptionally an initiator, or c-i) a carrier and an impregnation solution,forming an impregnated carrier, followed by mixing the impregnatedcarrier with one or more monomer species and optionally an initiator, toform a monomer-containing mixture, where said monomer species is solublein the polar solvent and has carbon-carbon unsaturation and at least onefunctional group comprising at least one heteroatom; and II)polymerizing at least a portion of said monomer species in themonomer-containing mixture to form a polymerized product; III) when I)does not include at least one phosphorus compound, at least one GroupVIB metal compound, and at least one Group VIII metal compound,contacting an impregnation solution and the monomer-containing mixtureduring the polymerizing in II); to form the supported catalyst, wherethe molar ratio of phosphorus to Group VIB metal is about 1:1.5 to lessthan about 1:12, where the molar ratio of the Group VIB metal to theGroup VIII metal is about 1:1 to about 5:1, where said impregnationsolution comprises a polar solvent, phosphorus, at least one Group VIBmetal, and at least one Group VIII metal, where a polymer is formedduring the polymerizing and the polymer has a carbon backbone, andcomprises functional groups having at least one heteroatom, and thepolymer loading is about 1.5 wt % or more, relative to the total weightof the other components in the catalyst.
 10. A supported catalyst as inclaim 9 wherein said Group VIB metal is molybdenum and/or tungsten,and/or wherein said Group VIII compound is nickel and/or cobalt.
 11. Asupported catalyst as in claim 9 wherein the catalyst has an averageparticle size of about 0.5 mm to about 5 mm.
 12. A supported catalyst asin claim 9 wherein the carrier is about 40 wt % to about 80 wt % of thecatalyst, relative to the total weight of the carrier, hydrogenationmetals, and phosphorus, where the hydrogenation metals and phosphorusare expressed as their oxides.
 13. A method for hydrotreating,hydrodenitrogenation, and/or hydrodesulfurization, which methodcomprises contacting a hydrocarbon feed and a catalyst of claim 9.